Aqueous dispersion



and Viskanol.

Patented Apr. 10, 1945 UNITED STATES PATENT OFFICE AQUEOUS DISPERSIONAndrew Szegvari, Fair-lawn, andAdrlan H. Feikert, Wadsworth, Ohio,assignors to American Anode, Inc., Akron, hio,'a

aware corporation of Del- TN'o Drawing. Original application March 23,

1940, Serial No. 325,652. Divided and this application July 4, 1944,Serial No. 543,488

14 Claims.

The invention relates to a method of treating a wide variety of fibrousmaterials including fibers in unfabricated as well as fabricated form inorder to produce fibrous articles and products eiihibiting to a highdegree certain desired properties of long life, wear resistance andresistance to a variety of other factors and influences involved in theusual service of the various articles and.

products. The invention also contemplates the treated fibrous productsobtained by practicing the method. More particularly, the inventioninvolves. the application to fibrous material of a coating deposit ofthe solids from an aqueous dispersion of polyisobutylene or similarmaterial preferably in admixture with certain other materials formodifying the characteristics of the 'polyisobut'ylene. The invention isespecially concerned with the treatment of fibrous materials withaqueous dispersions of certain tough, elastic and permanently resilient,high-molecular weight polymers of isobutylene and analogous olefins.

There are now available on the market in this country under thetradename Vistanex certain permanently resilient parafllnic materialsprepared by polymerizing olefins of low molecular 2 weight. Similarmaterial have also been sold under other trade-names including VispronaPOnly meager information concerning these commercial products has beenmade public, but it is understood that they are prepared by polymerizingcertain vapor fractions produced Thus, it appears that fractionscontaining considerable quantities of isobutylene possibly admixed withother olefins and ism-olefins of similar relatively low molecularweights may be polymerized 000 to 30,000 are liquid or liquid-like innature. The higher polymers having average molecular weights in therange extending from the region of 25,000 to 30,000.11p to 100,000 or200,000 or even 500,000 are quite diiierent in many physical prop-.erties and are permanently resilient solids as distinguished from theliquid and liquid-like polymers in the lower range of average molecularweights. InU. S. Patent No. 2,138,895 assigned to the manufacturersinthis country of Vistanex', the term "plastic is] applied to the lowerrange of liquid-like polymers while, in contradistinction, the termfelastic is applied to the re- 'silient polymers in the higher range ofaverage 'molecular weights.

The liquid and liquid-like plastic polymers in' the lower molecularweight range may be dispersed directly in water by commonlyused methodsof dispersing (emulsifying) insoluble liquid materials in water. On'thecontrary, it is difllcult in cracking petroleumto make cracked gasoline.

under suitable conditions to produce a variety of polymers of muchhigher molecular weights. .Apparently depending somewhat upon theparticular method of polymerization employed, the polymers well as guttapercha and balata), ester gum,

may consist practically, entirely of polymerized to prepare asatisfactory dispersion of the higher molecular weight polymers becauseof their permanently resilient and non-plastic nature. However, incertainother patent applications here- 5 inafter identified, we havedescribed methods by which the resilient solid polymers may be disperseddirectly in water to produce excellent'colloidal dispersions. Referenceis here made to the other'applications for details of the dispersingprocedures but it may be noted that one of the preferred proceduresinvolves the use of acon- .iunctive material such as a rubber (which isunderstood to include both natural and synthetic rubbers and rubber-typematerials, including pecifically natural crude rubber, rubbers in theform of'latex and artificial dispersions, reclaimed rubhers, butadienerubbers, and polychloroprene, as

asphalt, rubber derivatives prepared by treating rubber with sulfonic'acids, rubber degradation product obtained by dry distilling rubber andin- 'cluding both the volatile oils and the solid residues so produced,chlorinated diphenyl, chlorinated naphthalene, rosin, poly-ethylenedihalides "such as the commercialproduct' "A. X. F)? and like materials.All these materials may themselves be artificially dispersed in waterand all of them are compatible and capable of being homoo geneouslyblended with the hydrocarbon polymerization products being dispersed.For the sake of brevity. they have been termd .conjunctive materials asthey are now believed to function at least in part to promote a unionbetween the more inert polymerized solid hydrocarbon and the dispersing,agents and/or 'to promote a Such conjunctive materials are mixed withthe resilient polymers and the mixture is dispersed so that theconjunctive material appears with the polymer in the dispersed solidparticles. The polymer is present in the dispersed particles in a,resilient solid state.

We have found that such dispersions'of resilient, olid polyisobutyleneand similar materials preferably in admixture with one or moreconjunctive materials are especially useful for treating a wide varietyof fibrous materials.

Such dispersions have been mixed in quantities fabric. At the same time,the treatment must varying from 3% to-50% with paper pulp to pro I ducepaper greatly improved in strength and fiexibility as well as inresistance to water and chemicals. Somewhat similarly the dispersionshave been mixed with comminuted leather fibers or cotton or other fibersand formed into a sheet and dried to make artificial leather surpassingprior hibits exceptional strength and low permeability to gases.-Leathergoods in general, and conveyor and transmission belts of bothleather and fabric, are improved by treatment with the dispersions.

A. mass of glass wool in suitable form impregprovides an efilcientfilter for air-conditioning systems and especially for filteringcorrosive liquids or gases. Woven glass textile tapes impregnated withthe dispersions are especially useful for heat-resistant gaskets and asprotective coatings for plating racks used in chromium and other platingbaths. The dispersions are also valuable for treating clothing to beworn for protection against toxic gases and corrosive chemicals.

Emulsions or dispersions of the liquid-like polymers of isobutylene andalso dispersions of the resilient polymers prepared without the use ofconjunctive agents are satisfactory to some degree in practically allthe foregoing applications, and, in some cases, areequally assatisfactoryas the dispersions containing conjunctive materials.

-Gene'rally, however, the dispersions of resilient solid polymersassociated with conjunctive materials are definitely superior fortreating fibrous materials and are preferred for most uses in thatfield.

Aqueous dispersions-of polyisobutylene of the,

character described have thus far, found their widest application in thetreatment of womens silk and synthetic silk or rayon hosiery for the.purpose of improving the life and wear charac-- teristics of the hose;Many treatments for this purpose have been suggested from time to time,including treatments with rubber, with rubberderivatives, and with avariety of different natural and synthetic resins in many differentforms and including an equally wide variety of processes nated with sucha dispersion of polyisobutylene A washings.

not stiffen the hose to any substantial degree, must not alter thenatural silky feel unduly, and

must not impart any undesirable odor to the hose norimpair theirappearance. These requirements are to some extent seemingly mutuallyinconsistentand contradictory and no material or treating process hasheretofore been suggested or devised which satisfactorily meets all therequirements. Resins generally tend to stiffen the hose and attempts atplasticization have not been effective in relieving such stiffness.'Rubher, while sufficiently flexible; involves undesira ble odors andsurface characteristics imparting an undesirable feel to the hose. Othermaterials which have been proposed present similar undesirable features.

We have found that silk and other sheer hosiery may be treated withaqueous dispersions of the high molecular weight resilient, solidpolymers of isobutylene, preferably. in association with a conjunctivematerial of the character hereinabove described, and that-the treatedhose exhibit exceptional flexibility, excellent resistance to snagging,tearing, running and laddering, unusually long life, and good resistanceto repeated Also, the treated hoseare satisfactorily free ofobjectionable odors and undesirable surface characteristics such astackiness. Ithas further been found that especially satisfactoryreenforcement and surface characteristics are obtained if the treatingdispersion also contains a tack-destroying material of a resinous.nature such as a, phenolic resin, shellac, or a copolymer of butadieneand acrylic nitrile such as the commercial product Perbunan." Suchtack-destroying resins preferably areincorporated in the treatingdispersion in. quantities varying from 5% to 25% by weight.

The exceptionally satisfactory results obtained in treating silk hosieryaccording to the present invention appear to resultin part from themodifying effects of added materials, especially the conjunctivematerials and the tack-destroying dyed, although satisfactory resultsmay be obtained by treating dyed hose provided the dye materials foreach gallon of water:25 c. cl of 20% potassium oleate solution, 20 c. c.of a'15% solution of the commercial product known as Immersol TX, 15 c.c. of the synthetic saponaceous material sold as Aquarex D and 5 c. c.of 28% ammonium hydroxide solution. The soaps and ammonium hydroxide, ofcourse, may be replaced by other. well-known soaps and alkaline "soapsolution as a part of the regular manufacturin procedure. In treatingsuch hose according to the present invention, the' introfying solutiontreatment may be dispensed with in many cases as the neutral soaptreatment has a similar although somewhat less efllcient introfyingeffect. More uniform results are attained-if the introfy-' ing treatmentis employed whether or not the hose have been treated with soap or thelike.

The-prepared hose then are immersed in an aqueous dispersion of solid,resilient polyisobutylene prepared according to the method of ourapplications hereinafter identified and preferably containing aconjunctive material and a tack destroying material as well as otherincidental" compounding materials. For example, a satisfactory treatingdispersion may be prepared by admixing 100 parts by weight of "VistanexHigh Molecular Weight (a resilient solid polymer of isobutylene statedto have an average molecular .weight of around 200,000)" and 17 parts ofpremasticated crude Hevea rubber as a conjunctive material anddispersing the mixture according to a the procedure described in ouraforementioned applications. There is then preferably added to thedispersion as a tack-destroying material 15 vulcanize the rubberconjunctive material prescut, as well as an age-resistor for therubber.- Such materialsmay be added according to wellknown rubberdispersion compounding practice.

In the illustrative example, the vulcanizing agents may include 2 partsby weight of sulfur, 3.3 parts of organic accelerator of vulcanization,and 2 parts of zinc oxide. 0.4 part of'a commercial age-resistor such asAgeRite White. (sym. di

parts by weight of f-phosphotex, a phosphate salt,

stabilizer. The treating dispersion may contain from to 50% total solidsby weight but preferably contains in the neighborhood of 20% to ropreneor butadiene rubber or similar synthetic rubber or rubber-typematerial(all within the generic term "a rubber" and the corresponding pluralterm rubbers; as herein employed and as previously indicated) in orderto eliminate any trace of natural; crude rubber odor and tackiness.-'

The hose are permitted to remain in the treating dispersion for about-30 seconds after which they are removed together with a considerablequantity of the dispersion in association with the hose in anuncoagulated condition. The hose press a substantial part of theassociateddispersion, and the hose are then conveyed between forcefulblasts of compressed air or the like to blow bridgingiilrns fromtheinterstices of the 5 hose fabric. It is important that the removal ofthe excess uncoagulated dispersion be effected before any substantialcoagulation has occurred. Otherwise a non-uniform coating is produced.The treated hose then are mounted on conveniu tional boarding forms" andare dried for 5 minutes at 150F, toeffect coagulation of the dispersionon the fibers. If desired, the coagulation may be effected by placingthe treated hose in a chamber filled with vapors of a coagulant such asformic-acid or acetic acid. The coagulated' rubber is then vulcanized byheating for 30 minutes at 220 F. Thereafter, the hose are washed in a0.5% mild soap solution at 90 F. rinsed in fresh water, centrifuged andagain dried. The

hose are then dyed according to usual practices unless pie-dyed hosehave been treated.

The individual yarns and fibers or the treated mhose are covered with acoating which is .of the order of only 5 microns in thickness (which isunderstood to include variations of from 3 to 10 microns unlessotherwise indicated). Notwithstanding the extreme thinness ofthecoating, the life and wear characteristics of the hose are improvedremarkably and none of the undesirable features of prior treatments arepresented.

'While the detailed procedure hereinabove d'escribed has been developedespecially for treating silk, rayon, .nylon and other sheer knittedhosiery, substantially the same procedure may be employed advantageouslyfor treating a variety of textile and other fabric materials. Thusfabrics and other fibrous structures of wool, cotton, silk,glassand'synthetic yarns or threads such as "nylon" and rayon may betreated effectively 40 by the procedure described, or the treatingdispersions may be simply spread, brushed, or transferred to the fibrousmaterial by a, transfer roll. Similarly, many of the features of thehosiery treatment may be applied advantageously'to the 4.1 treatmentof'the' variou fibrousmaterials described in the earlier paragraphsofthis specification. All such applictaions and many variations'indetails of the procedures and materials described are within the spiritand scope of the invention asdefined by the appended claims.

A part of the subject matter hereindisclosed is claimed in ourconcurrently filed application Serial No. 543,489. filed July 4, 1944.

This-application is a division of our co-pending application Serial No.325,652'filed March 23, 1940, which was a continuation-in-part of ourearlier co-pending application Serial No. 308,220 filed December 8, 1939(now U. S. Patent No. 2,194,958 granted March 26, 1940) which, in turn,

00 was a continuation-in-part of a co-pending application Serial No.83,356, filed June 3, 1936.

We claim:

1. As a composition of matter, an aq'ueousdispersion containingsubstantial quantities of a resilient solid high molecular'weightpolymerization product having parafli'nic characteristics prepared bypolymerizing a mono-olefin of low molecular weight; shellac; and arubber material selected from the class consisting of natural rub- 7her, polychloroprene, reclaimed rubber. and butadiene-synthetic rubberother than a copolymer of weight not less than substantially 30,000.

7. 2. 'As a composition of matter, an, aqueous dispersion containingsubstantial quantities of a resilient solid high molecular weightpolymerization product'having parafiinic characteristics prepared bypolymerizing a mono-olefin of low molecular weight; shellac; and naturalrubber;

the polymerization product being one having an average molecular weightnot less than substantially 30,000. I

3. As a composition of matter, an aqueous dispersion containingsubstantial quantities of a resilient solid high molecular weightpolymerization product having paraffinic characteristics prepared bypolymerizing a mono-olefin of low,

molecular weight; shellac; and a butadiene synthetic rubber other than acopolymer of butadiene and acrylic nitrile; the polymerization product8. As a composition or matter, an aqueous dispersion containingsubstantial quantities of shel lac; a resilient solid high molecularweight polymer of isobutylene having an average molecular weight. notless than substantially 30,000; and polychloroprene. I

9. As a composition of matter, an aqueous dispersion containingsubstantial quantities or shellac; a resilient solid high molecularweight polymer of isobutylene having an average molecular weight notless than substantially 100,000; and a rubber material selected from theclass consisting of natural rubber, polychloroprene, reclaimed rubberand a butadiene synthetic rubber other molecular weight; shellac; andpolychloroprene;

the polymerization product being one having an average molecular weightnot less than substan tially 30,000.

5. As a composition of matter, an aqueous dispersion containingsubstantial quantities of shellac; a resilient solid high molecularweight polymer of isobutylene having an average molecular weight notless than substantially 30,000; and a rubber material selected from theclass consisting of natural rubber, polychloroprene, reclaimed rubberand butadiene synthetic rubber other than a copolymer of butadiene andacrylic nitrile. r

6. As a composition of matter, an aqueous clispersion containingsubstantial quantities or shellac; a resilient solid high molecularweight polythan a copolymer of butadiene and acrylic nitrile.

10. As a composition of matter, an aqueous dispersion containingsubstantial quantities of shellac; a resilient solid high molecularweight polymer of isobutylene having an average molecular weight notless than substantially 100,000; and

natural rubber.

11. As a composition of matter, an aqueous dispersion containingsubstantial quantities of shellac; a resilient solid high molecularweight polymer of isobutylene having an average molecular weight not"less than substantially 100,000; and a butadiene synthetic rubber otherthan a copolymer of butadiene and acrylic nitrile.

12. As a. composition of matter, an aqueous dis= persion containingsubstantial quantities of shel lac; a resilient solid high molecularweight polymer of isobutylene having an average molecular weight notless than substantially 100,000; and polychloroprene.

13. A composition comprising an aqueous dispersion containingsubstantial quantities of shelmer of isobutylene having an averagemolecular Weight not less than substantially 30,000; and natural rubber.

'7. As a composition of matter, an aqueous dispersion containingsubstantial quantities of shellac; a resilient solid high molecularweight poly mer of isobutylene having an average molecular weight notless than substantially 30,000; and a butadiene synthetic rubber otherthan a copolymer of butadiene and acrylic nitrile.

lac and colloidally dispersed solid particles of a resilient solidpolymer having an average olecular weight not less than substantially30,000 prepared by polymerizing a material, consisting principally ofisobutylene.

14. A composition comprising anaqueous clis- ANDREW SZEGVARI. ADRIAN H.'FEIKERT.

